JP6952744B2 - Penetration - Google Patents

Description

The present invention is a penetration portion particularly passing through a housing portion of a housing, particularly a battery cell housing, through which the housing portion is penetrated by at least one essentially pin-shaped conductor in a glass material or glass ceramic material. With respect to a penetration having one opening.

A battery in the sense of the present invention is understood to be a disposable battery that is discarded and / or recycled after being discharged, or a storage battery.

Batteries, preferably lithium-ion batteries, are designed for a variety of applications, such as portable electronics, mobile phones, machine tools and especially electric vehicles. The battery can replace conventional energy sources such as lead acid batteries, nickel cadmium batteries or nickel metal hydride batteries.

Lithium-ion batteries have been known for many years. See, for example, "Handbook of Batteries", edited by David Linden, 2nd Edition, McGrawhill, 1995, Chapters 36 and 39.

Various aspects of the lithium ion battery are described in numerous patent documents. For example, US Pat. No. 961,672, US Pat. No. 5,952,126, US Pat. No. 5,900,183, US Pat. No. 5,874,185, US Pat. No. 5,849,434, US Pat. Patent No. 5,853,914 and US Pat. No. 5,773,959 can be mentioned.

Lithium-ion batteries, especially for use in an automotive environment, typically have a large number of separate battery cells, which are connected in a row to each other. Battery cells connected in series or in a row with each other are grouped into so-called battery packs, and several battery packs are grouped into a battery module, also called a lithium-ion battery. Each individual battery cell has an electrode that is derived from the battery cell housing.

In order to use a lithium-ion battery in an automobile environment, a number of problems such as corrosion resistance, accident resistance (Bestaendigkeit bei Unfall) or vibration strength must be solved. One of the further problems is the airtightness of the battery cell over a long period of time. Airtightness can be compromised by loosening in the battery cell electrodes or within the battery cell electrode penetrations. Such loosening can be caused, for example, by loads of temperature changes and mechanical stress changes such as vehicle vibrations or aging of plastics. Shorts or temperature changes in the battery or battery cell can shorten the life of the battery or battery cell.

To ensure better accident resistance, German Patent No. 101 05 877 (A1) proposes, for example, a housing for a lithium-ion battery, in which case the housing is open on both sides. Includes a metal jacket that is designed to be closed. The current connection or electrodes are insulated by plastic. The drawbacks of the plastic insulation are limited heat resistance, limited mechanical resistance, aging and uncertain airtightness throughout life. Therefore, in the conventional lithium ion battery, the current penetration portion is non-airtightly incorporated in, for example, the cover portion of the Li ion battery. In addition, the electrodes are a crimped, laser welded joint with additional insulation within the interior space of the battery.

A further problem with prior art lithium-ion batteries is that the battery cell has a large structural space and, based on the large current, heats up very quickly due to resistance loss, thus causing temperature changes.

From German Patent No. 27 33 948 (A1), an alkaline battery in which an insulator such as glass or ceramic is directly bonded to a metal portion by melt bonding is known.

One of the metal parts is electrically bonded to the anode of the alkaline battery and the other is electrically bonded to the cathode of the alkaline battery. The metal used in German Patent No. 27 33 948 (A1) is iron or steel. Light metals such as aluminum are not described in German Patent No. 27 33 948 (A1). The melting temperature of the glass or ceramic material is also not shown in German Patent No. 27 33 948 (A1). The alkaline battery described in German Patent No. 27 33 948 (A1) is a battery containing an alkaline electrolyte, the electrolyte of which is sodium hydroxide or potassium hydroxide according to German Patent No. 27 33 948 (A1). Is. No reference to Li-ion batteries can be found in German Patent No. 27 33 948 (A1).

From German Patent No. 698 04 378 (T2) or European Patent No. 0 885 874 (B1), methods for producing asymmetric organic carboxylic acid esters and methods for producing water-free organic electrolytes for alkaline ionized batteries It is known. Electrolytes for rechargeable lithium-ion cells are also described in German Patent No. 698 04 378 (T2) or European Patent No. 0 885 874 (B1).

The material for the cell socket for accommodating the through contact is not described, only the material for the connecting pins is described, which may consist of titanium, aluminum, nickel alloy or stainless steel.

German Patent No. 699 23 805 (T2) or European Patent No. 0 954 045 (B1) describes RF-penetrations with improved electrical effectiveness. The penetrations known from European Patent No. 0954 045 (B1) are not glass-metal penetrations. European Patent No. 0 954 045 (B1) is disadvantageous, for example, in glass-metal penetrations formed directly in the metal walls of the packaging. It is stated that such RF-penetrations are not robust due to the weakening of the glass.

German Patent No. 690 230 71 (T2) or European Patent No. 0 412 655 (B1) describes glass-metal penetrations for batteries or other electrochemical cells, where as glass. _{Glass with a SiO 2} content of about 45% by weight is used, and alloys containing molybdenum and / or chromium and / or nickel are used as the metal. The use of light metals, as well as the melting temperature of the glass used, is rarely described in German Patent No. 690 23 071 (T2). In German patent 690230 71 (T2) or European patent 0 412 655 (B1), the material for pin-shaped conductors is also an alloy containing molybdenum, niobium or tantalum.

Glass-metal penetrations for lithium-ion batteries have become known from US Pat. No. 7,687,200. In US Pat. No. 7,687,200, the housing was made of special steel and the pin-shaped conductor was made of platinum / iridium. U.S. Pat. No. 7,687,200 describes glass TA23 and CABAL-12 as glass materials. In that case, US Pat. No. 5,015,530 is a CaO-MgO-Al ₂ O _3- B ₂ O ₃ system having a melting temperature of 1025 ° C or 800 ° C. Further, from US Pat. No. 5,015,530, a glass composition for a glass-metal penetration part for a lithium battery is known, and the glass composition is CaO, Al ₂ O ₃ , B _2. It _{contains O 3} , SrO and BaO, the melting temperature of which ranges from 650 ° C to 750 ° C, and is therefore too high for use with light metals.

From U.S. Pat. No. 4,841,101, a penetration is known in which essentially pin-shaped conductors are made of glass and are glazed to a metal ring. The metal ring is then reattached to the opening or perforation of the housing and is joined particularly tightly to the inner wall or perforation by soldering, eg, after the solder ring has been tightened. The metal ring is made of a metal that has essentially the same or similar coefficient of thermal expansion as the glass material to compensate for the high coefficient of thermal expansion of aluminum in the battery housing. In the embodiment described in US Pat. No. 4,841,101, the length of the metal ring is always shorter than the perforation or opening of the housing. U.S. Pat. No. 4,841,101 does not describe glass compositions, nor does it describe the special use of penetrations, for example for batteries, especially Li-ion batteries.

U.S. Pat. No. 961,672 U.S. Pat. No. 5,952,126 U.S. Pat. No. 5,900,183 U.S. Pat. No. 5,874,185 U.S. Pat. No. 5,849,434 U.S. Pat. No. 5,853,914 U.S. Pat. No. 5,773,959 German Patent No. 101 05 877 (A1) German Patent No. 27 33 948 (A1) German Patent No. 698 04 378 (T2) European Patent No. 0 885 874 (B1) German Patent No. 699 23 805 (T2) European Patent No. 0 954 045 (B1) German Patent No. 690 230 71 (T2) European Patent No. 0 412 655 (B1) U.S. Pat. No. 7,687,200 U.S. Pat. No. 5,015,530 U.S. Pat. No. 4,841,101 German Patent No. 10 2009 011 182 (A1)

"Handbook of Batteries", edited by David Linden, 2nd Edition, McGrawhill, 1995, Chapters 36 and 39 R. Goerke, K.K. -J. Leers: Keram. Z. 48 (1996) 300-305

Therefore, an object of the present invention is to provide a penetration portion that avoids the problems of the prior art.

In the present invention, this task is preferably made up of light metals that melt at low temperatures, preferably aluminum, aluminum alloys, magnesium, magnesium alloys, titanium, titanium alloys, or metals, especially steel, specialty steels, especially stainless steel or AlSiC. This is solved by penetrating conductors in glass or glass ceramic materials, especially pin-shaped conductors, especially in the case of penetrations, especially through openings in the housing portion of the housing for battery cells.

The present invention is characterized in that the penetration includes at least one conductor, particularly a pin-shaped conductor, and a support, particularly a ring-shaped support. In the form of a penetration through the housing portion by an additional support in which the conductor, especially the pin-shaped conductor material, is glassed therein, the penetration is pre-created, i.e. the pin material is glass in the support. It can be attached and subsequently incorporated into the housing portion, especially in the battery cell. In that case, the support can be optimally adapted to the respective manufacturing techniques and forms of the penetration and the manufacturing techniques and forms of the housing portion. In particular, by making it in advance, it is possible to use a heating device that is considerably smaller than the case where the glass is directly attached to the housing portion. This is because it is not necessary to heat the entire housing portion, for example, in an oven, and only the support having a considerably small size needs to be heated. In addition, support and conductors, in particular of such forms in which it is possible to pre-create penetrations consisting of essentially pin-shaped conductors, allow the penetrations to be cost-effectively introduced into the openings of the housing portions. This is possible, for example, in a one-step process, taking advantage of the cold fixability of the housing portion, for example. Specifically, this means that an opening is first introduced into the housing portion, for example, in the cover, by, for example, drilling. Since it is not heated, its housing is cold-fixed. On the other hand, the support is soft because it is heated together with the glass material or the glass ceramic material when the pin-shaped conductor is glassed. In this method, it is possible to generate a structurally fixed battery cell housing, especially in the region of the penetration. This is because, unlike, for example, direct glass attachment to the housing portion, there is no loss of cold fixing of the housing portion, especially the cover portion. A further advantage is that the material strength of the housing portion can be selected to be significantly lower than that of the glassed support. For example, the material thickness of the housing portion may be 1.5 mm or less, whereas the support includes a thickness of 2.0 mm, particularly 3.0 mm or more, for strength reasons. The material thickness of the housing or housing portion is preferably 1 mm to 3 mm, preferably 1.5 mm to 3 mm. The thickness of the support is 2 mm to 6 mm, preferably 2.5 mm to 5 mm. In that case, the thickness of the support is always selected according to the material thickness of the housing or housing portion to which the penetration is attached, especially the battery cover. On the other hand, in the case of direct glass attachment, an unnecessarily thick material thickness would be required.

A further advantage is that the materials for the support and housing parts can be selected separately, especially for material quality and alloy selection. The penetration can be airtightly joined to the housing portion together with the support by welding, soldering, pushing, flanged or shrinking. When joining the penetrations to the housing parts, for example by welding, care should be taken to keep the temperature supply as low as possible to avoid damage to the glass or glass ceramic materials. In the present application, airtightness means a helium leakage rate of less than ^{1 × 10 8 mbar l / sec.} Unlike the prior art in which a plastic seal must be provided for the penetration in a multi-step process, the airtight bonding of the penetration part and the housing portion according to the present invention can occur in only one simple method step.

Further, the selection of the support can be made in consideration of the material of the housing portion as well as the edge forming portion and the material hardness, particularly the method of sealing the housing. If the battery cell housing is made of, for example, aluminum, aluminum can also be selected as the material for the support.

Furthermore, in addition to penetrating the housing portion of the housing, it is possible to introduce additional functions, such as safety valves and / or battery inlets, into the battery cell.

In the first embodiment of the present invention, the housing portion and / or the support, preferably the essentially ring-shaped support, is made of metal as a material, particularly titanium, titanium alloy, magnesium, magnesium alloy, aluminum alloy, aluminum, AlSiC. Light metals such as, but also other steels, stainless steels or special steels are particularly preferred. For example, Ti6246 and / or Ti6242 can be used as the titanium alloy. Since titanium is a biocompatible material, it has been used for medical purposes, for example in prostheses. Similarly, due to its special strength, durability and light weight, it is preferred for special applications such as racing, but also for other aviation and space applications.

High alloy tool steel, which is later intended for heat treatment, can also be used for the support and / or housing portion. The special steels that can be used are, for example, X12CrMoS17, X5CrNi1810, XCrNiS189, X2CrNi1911, X12CrNi177, X5CrNiMo17-12-2, X6CrNiMoTi17-12-2, X6CrNiTi1810 and X15CrNiSi25-20, X10CrNi1808, X2TiCrNi1808, X2CrNi1808 -2. Special steels, especially Euro, as materials for supports and / or housing parts, especially battery cell housings, so that particularly good weldability can be provided during both laser and resistance welding. Cr—Ni steels having material numbers (WNr.) 1.4301, 1.4302, 1.4303, 1.4304, 1.4305, 1.4306, 1.4307 according to −Norm (EN) are used. As standard steel, St35, St37 or St38 can be used.

For pin-shaped conductors, especially when the pin-shaped conductor is connected to the cathode of an electrochemical cell or battery cell, copper (Cu) or copper alloy is used, and the conductor, especially the pin-shaped conductor, When connected to an anode, aluminum (Al) or an aluminum alloy is used. Other materials for pin-shaped conductors are magnesium, magnesium alloys, copper alloys, CuSiC, AlSiC, NiFe, copper cores, ie NiFe jackets with copper interiors, silver, silver alloys, gold, gold alloys and cobalt- It can be an iron-alloy.

Especially as aluminum or aluminum alloys for conductors:
EN AW-1050 A
EN AW-1350
EN AW-2014
EN AW-3003
EN AW-4032
EN AW-5019
EN AW-5056
EN AW-5083
EN AW-5556A
EN AW-6060
EN AW-6061

Especially as copper for conductors:
Cu-PHC 2.0070
Cu-OF 2.0070
Cu-ETP 2.0065
Cu-HCP 2.0070
Cu-DHP 2.0090

In this application, a light metal is understood to be a metal having a specific weight of less than ^{5.0 kg / dm 3.} In particular, the specific weight of the light metal is in the range of ^{1.0 kg / dm 3} to 3.0 kg / dm ^3.

Additionally, light metal conductor, for example, when used as a material for the pin-shaped conductor or electrode junction part, the light metal is further noted, of ^{5 × 10 -6 S / m~50 ×} 10 -6 S / m It features a range of specific conductivity. Further in addition if used in a pressurized glass penetrating portion (Druckglasdurchfuehrung), expansion coefficient in the range of 20 ° C. to 300 ° C. alpha is in the range of ^{18 × 10 -6 / K~30 × 10} -6 / K Is.

In general, light metals have a melting temperature in the range of 350 ° C to 800 ° C.

Preferably, the support is configured as a ring-shaped support, preferably in a circular shape, but also in an elliptical shape. A glass material or glass ceramic in which the through-part is introduced into the opening, especially the battery cell cover has a narrow and long form and penetrates the housing with the pin-shaped conductor in the opening. The elliptical form is particularly preferred when the material is completely introduced between the support and the pin-shaped conductor. Such a form makes it possible to pre-create a penetration consisting of an essentially pin-shaped conductor and an essentially ring-shaped support.

Preferably, in one form, the glass material or glass ceramic material is selected such that it has a melting temperature lower than the melting temperature of the support and / or essentially pin-shaped conductor. Particularly preferred in this case is a glass composition or glass-ceramic composition having a low melting temperature, preferably a composition containing the following components:
P ₂ O ₅ 35-50 mol%, especially 39-48 mol%,
Al ₂ O ₃ 0~14mol%, particularly 2~12mol%,
B ₂ O ₃ 2 to 10 mol%, especially 4 to 8 mol%,
Na ₂ O 0 to 30 mol%, especially 0 to 20 mol%,
M ₂ O 0 to 20 mol%, especially 12 to 20 mol% (where M = K, Cs, Rb may be),
PbO 0-10 mol%, especially 0-9 mol%,
Li ₂ O 0 to 45 mol%, especially 0 to 40 mol%, preferably 17 to 40 mol%,
BaO 0 to 20 mol%, especially 0 to 20 mol%, preferably 5 to 20 mol%,
Bi ₂ O ₃ 0~10mol%, in particular 1 to 5 mol%, preferably 2~5mol%.

Particularly preferred are compositions containing the following components:
P ₂ O ₅ 38-50 mol%, especially 39-48 mol%,
Al ₂ O ₃ 3-14 mol%, especially 2-12 mol%,
B ₂ O ₃ 4-10 mol%, especially 4-8 mol%,
Na ₂ O 10-30 mol%, especially 0-20 mol%,
K ₂ O 10-20 mol%, especially 12-19 mol%,
PbO 0-10 mol%, especially 0-9 mol%.

The above-mentioned glass composition is not only excellent at low melting temperature and low Tg, but also has sufficiently high durability against battery electrolytes, and in that respect, guarantees the required long-term durability. Is excellent in.

The glass material shown as preferred is a stable phosphate glass having a significantly lower total alkali content than known alkali phosphate glasses.

The normally high crystal stability of phosphate glass ensures that melting of the glass is not hindered, even at temperatures typically <600 ° C. This allows the glass composition shown to be used as a glass solder, since melting of the glass composition is usually not prevented even at temperatures <600 ° C.

The glass composition has Li incorporated into the glass structure. This makes the glass composition particularly suitable for Li ion battery devices containing Li containing a 1: 1 mixture of ethylene carbonate and dimethyl carbonate, eg _{, an electrolyte based on a 1M LiPF 6 solution.}

Particularly preferred is a glass composition that is low in sodium or free of sodium. This is because the diffusion of alkaline ions occurs in the order Na +> K +> Cs +, so sodium-poor or sodium-free glass is used for electrolytes, especially those used in Li-ion batteries. This is because it is particularly durable.

Further, the glass composition of the seed, in the range of ^{20 ℃ ~300 ℃> 14 × 10} -6 / K, in particular ^{15 × 10 -6 / K~25 × 10} -6 / thermal expansion coefficient in the range of K alpha Is shown. A further advantage of the glass compositions shown above is that the glass can be melted in a gas atmosphere that is not a protective gas atmosphere, along with the light metal or metal of the enclosing, especially the conductor in the form of a pin. Unlike conventional methods, no vacuum is required for Al melting. Rather, such melting can also be done in air. _{N 2} or Ar can be utilized as the protective gas for both types of melting. As a pretreatment for melting, metals, especially light metals, are cleaned and / or etched if predetermined oxidation or coating is required. During the process, temperatures between 300 ° C and 600 ° C are used with heating rates of 0.1 to 30 C / min and holding times of 1 to 60 minutes.

The melting temperature is, for example, via the Halbukugel temperature, the entire disclosure of which is incorporated herein by R. et al. Goerke, K.K. -J. Leers: Keram. Z. 48 (1996) 300-305, or as described in DIN 51730, ISO 540 or CEN / TS 15404 and 15370-1. The measurement of hemispherical temperature is described in detail in German Patent No. 10 2009 011 182 (A1), the entire disclosure of which is incorporated in this application. According to German Patent No. 10 2009 011 182 (A1), the hemispherical temperature can be determined by microscopy using a heated on-board microscope. They indicate the temperature at which the original columnar test pieces melt together into a hemispherical mass. Hemispherical temperature can be associated with a viscosity of about log η = 4.6 dPas, as can be inferred from the corresponding literature. When crystal-free glass is melted, for example, in the form of glass powder, cooled again and solidified, it can usually be melted again at the same melting temperature. This means that for bonding with crystal-free glass, the operating temperature at which the bonding can be exposed for extended periods of time must be below the melting temperature. Glass compositions such as those used in the present invention are often made from glass powders that are often melted to form a bond with a component to be joined under thermal action. The melting temperature or melting temperature usually corresponds approximately to the height of the so-called hemispherical temperature of the glass. Glass with a low melting temperature or melting temperature is also referred to as glass solder. In such cases, instead of the melting temperature or melting temperature, the soldering temperature or soldering temperature is mentioned. The melting or soldering temperature can deviate from the hemispherical temperature by as much as ± 20C.

The housing portion of the battery housing or battery cell housing has outside and inside, and the support of the penetration is joined to the inside or outside of the housing portion, in particular by, for example, Boerdeln, welding, pushing, soldering or shrinking. It is particularly preferable that it is done.

To this end, the support has a protrusion, one portion of the support engages the opening of the housing portion, and the other portion of the support projects above the opening, inside or outside the housing portion. It is particularly preferred that it rests on or where it can be joined to the housing portion.

In a further formed embodiment, the pin-shaped conductor also includes a head portion or a fixed portion. The head portion may have a protrusion protruding above the head portion. The protrusions can serve to provide Zentrierung of electrodes or electrode junctions. In the embodiment having a head portion, the electrode joining component or the battery electrode can be connected to the head portion extending inside the battery cell housing.

The protrusions can have an outer contour that is separate from the pin-shaped conductor. For example, a pin-shaped conductor could have an elliptical outer contour, whereas a protrusion could have a ring-shaped outer contour. The dimensions do not necessarily have to be the same.

In addition to the penetrations, the present invention also provides housings, especially for electrical storage batteries, especially battery cells. The housing comprises at least one housing portion with at least one opening, the through portion according to the invention having the opening of the housing portion having at least one pin-shaped conductor glazed in the support. It is characterized by accommodating.

Particularly preferably, the battery cell utilizing the housing is a battery cell for a lithium ion battery.

Further, the present invention provides a method of making a penetration having at least one essentially pin-shaped conductor, the method of which is:
With the steps of preparing conductors, especially pin-shaped conductors and supports,
Includes the step of glazing a conductor, especially a pin-shaped conductor, in a glass or glass ceramic material to a support to create a penetration for the housing portion of the housing, especially the battery cell housing. ..

In addition, a method of introducing a penetrating portion having a support into a housing component has been shown, in which a penetrating portion having a support and a conductor glass-mounted therein, particularly a pin-shaped conductor, are introduced. In particular, it is characterized by joining by welding, preferably laser beam welding, electron beam welding, ultrasonic welding, resistance welding, and otherwise by soldering, shrinking, pushing or flanged.

Hereinafter, the present invention will be described in detail with reference to Examples and Drawings, but the present invention is not limited thereto.

It is a figure which shows the 1st form of the penetration part by this invention which includes a metal pin and a support formed as a flange ring in a housing part. It is a figure which shows the 2nd form of the penetration part by this invention which has the support formed as a welding ring. FIG. 5 shows a third embodiment of penetration according to the invention in which the support is joined to the housing portion within the range of the opening by laser welding, soldering, shrinkage or electron welding. It is a figure which shows the 4th Embodiment of the penetration part by this invention which has a conical ring as a support attached to the opening of the housing part. It is a figure which shows one form of the penetration part by this invention which provided the elliptical pin-shaped conductor which has an elliptical head part. It is a figure which shows the further embodiment of the circular pin-shaped conductor which has a circular head part. It is a figure which shows the 4th Embodiment of the pin-shaped conductor which has a head part. It is a figure which shows the 1st Embodiment of the penetration part provided with a thermal barrier and a mechanical unloading. It is a figure which shows the 2nd Embodiment of the penetration part provided with a thermal barrier and a mechanical unloading. It is a figure which shows the battery cell which has the battery cell housing and the penetrating part which has a penetrating part but does not have a head part together with an electrode joining part. It is a figure which shows the battery cell which includes the battery cell housing and the penetrating part which provided the penetrating part which has the head part by this invention together with the electrode joining part. It is a figure which shows the battery cell which includes the battery cell housing and the penetration part which provided the penetration part by the further modification of this invention.

FIG. 1a shows a through portion 3 according to the invention that passes through a housing, preferably a housing for a storage battery, particularly a housing portion 5 of a battery cell for a lithium ion battery according to, for example, FIGS. 10a-12c.

In the following, examples of pin-shaped conductors having no head portion will be described, but even when this is not clearly stated, the examples also relate to pin-shaped conductors having a head portion. obtain.

The housing portion 5 includes an opening 7 provided in the housing portion. The opening 7 is introduced with a through portion according to the invention that includes a conductor, in particular a support that houses an essentially pin-shaped conductor 11, especially a ring-shaped support 9. The essentially ring-shaped support 9 is glassed with essentially pin-shaped conductors. In order to provide an airtight penetration of the support and additionally the essentially pin-shaped conductor 11 through the opening 7, the essentially pin-shaped conductor 11 is a glass stopper made of a glass material or a glass ceramic material. It is melt-sealed inside. That is, the support 9 and the essentially pin-shaped conductor 11 are combined with the glass 13. When using materials with different coefficients of expansion α, for example for supports, pin-shaped conductors and glass materials, so-called pressure glass penetrations can be provided. The advantage of the pressurized glass penetrating portion is that the glass stopper is prevented from being extruded from the support together with the metal focus even under a high load on the glass stopper, for example, under a pressure load. Preferably, the melting temperature of the glass or glass ceramic material is intended to be 20C to 100C below the melting temperature of the support 9 and / or pin-shaped conductor material. If the support 9 is made of a metal that melts at low temperatures, especially light metals, preferably aluminum, aluminum alloys, magnesium, magnesium alloys or AlSiC, titanium, titanium alloys, but also steel, stainless steel or specialty steels, preferably. As the glass material through which the conductor penetrates, a glass material containing the following components in the following mol% is used:
P ₂ O ₅ 35-50 mol%, especially 39-48 mol%,
Al ₂ O ₃ 0~14mol%, particularly 2~12mol%,
B ₂ O ₃ 2-10 mol%, especially 4-8 mol%,
Na ₂ O 0 to 30 mol%, especially 0 to 20 mol%,
M ₂ O 0 to 20 mol%, especially 12 to 20 mol% (where M = K, Cs, Rb may be),
PbO 0-10 mol%, especially 0-9 mol%,
Li ₂ O 0 to 45 mol%, especially 0 to 40 mol%, preferably 17 to 40 mol%,
BaO 0 to 20 mol%, especially 0 to 20 mol%, preferably 5 to 20 mol%,
Bi ₂ O ₃ 0~10mol%, in particular 1 to 5 mol%, preferably 2~5mol%.

In a particularly preferred embodiment, the glass composition comprises the following components in the following mol%:
P ₂ O ₅ 38-50 mol%, especially 39-48 mol%,
Al ₂ O ₃ 3-14 mol%, especially 4-12 mol%,
B ₂ O ₃ 4-10 mol%, especially 4-8 mol%,
Na ₂ O 10-30 mol%, especially 14-20 mol%,
K ₂ O 10-20 mol%, especially 12-19 mol%,
PbO 0-10 mol%, especially 0-9 mol%.

The glass compositions listed above are shown below in Table 1 with eight examples.

Special glass composition described above, a glass material, 20 ° C. at a temperature of to 300 ° C.> of 15 × ^{10 -6} / K range, preferably ^{15 × 10 -6 / K~25 × 10} -6 / K Very high thermal expansion, which is in the range, and thus in the range of thermal expansion rates of light metals such as aluminum for essentially pin-shaped conductors 11 penetrating the glass material, but other similar metals, such as copper. It is characterized by having a rate. For example, at room temperature, aluminum has a coefficient of thermal expansion α = 23 × ^10-6 / K, and copper has a ^{coefficient of thermal expansion of 16.5 × 10-6} / K. The melting temperature of the glass material is less than the melting temperature of the support and / or conductor material to prevent the light metal of the support and, in some cases, the metal pins from melting or deforming during glassing. The melting temperature of the glass composition is in the range of 250 ° C to 650 ° C. Glazing the essentially pin-shaped conductor 11 to the support 9 before attaching the penetration to the opening 7 heats the glass together with the conductor, especially the pin-shaped conductor, to the melting temperature of the glass. This is achieved by softening the glass material and enclosing the conductor, especially the pin-shaped conductor, in the opening so that it is in close contact with the support 9. As described above, for example, when aluminum is used as a light metal with a melting point T melting = 660.32 ° C. for the support 9, the melting temperature of the glass material is preferably in the range of 350 ° C. to 640 ° C. as described above. be. Preferably, the material of the pin-shaped conductor 11 is the same as the material of the support. This has the advantage that the coefficients of expansion of the support and the metal pins are the same. Pin-shaped conductors are made of materials such as aluminum, aluminum alloys, AlSiC, copper, copper alloys, CuSiC alloys or NiFe alloys, copper cores, ie NiFe jackets or CF25s with copper interiors, ie cobalt-iron alloys, silver, silver. Alloys, gold or gold alloys may be included. Pressurized glass penetration occurs when the coefficient of expansion α of the glass or glass ceramic material in the range of 20 ° C to 300 ° C does not exactly match the material of the support. In other cases, it is a so-called conforming penetration.

As the material for the support, light metals such as aluminum (Al), AlSiC, aluminum alloys, magnesium, magnesium alloys, titanium and titanium alloys are preferably used. Another material for the support is a metal such as steel, stainless steel, specialty steel or tool steel.

The melting temperature of glass or glass ceramic is the melting temperature of glass or glass ceramic, which softens the glass material and closely adheres to the metal to be bonded to the glass material, resulting in a bond between the glass or glass ceramic and the metal. Understood as temperature.

The melting temperature is, for example, via the hemispherical temperature, the entire disclosure of which is incorporated herein by R. et al. Goerke, K.K. -J. Leers: Keram. Z. 48 (1996) 300-305, or as described in DIN 51730, ISO 540 or CEN / TS 15404 and 15370-1. The measurement of hemispherical temperature is described in detail in German Patent No. 10 2009 011 182 (A1), the entire disclosure of which is incorporated in this application.

Glass solders known from German Patent No. 10 2009 011 182 (A1) relate, for example, to high temperature applications in fuel cells.

The phosphate glass composition described above has a Li content of up to 45 mol%, especially up to 35 mol%. Surprisingly, these glass compositions have crystallization stability. That is, in subsequent sintering steps, it does not show obstructive crystallization, especially less than 35 mol% crystallization, which is not significant.

The glass compositions listed above have Li incorporated into the glass structure. This makes the glass composition particularly suitable for Li-ion battery devices containing Li containing a 1: 1 mixture of ethylene carbonate and dimethyl carbonate, eg _{, an electrolyte based on a 1M LiPF 6 solution.}

Particularly preferred is a glass composition that is low in sodium or free of sodium. This is because the diffusion of alkaline ions occurs in the order Na +> K +> Cs +, so sodium-poor or sodium-free glass is used for electrolytes, especially those used in Li-ion batteries. This is because it is particularly durable.

Glass composition described above, has a> 14 × ¹⁰ -6 / K, in particular thermal expansion coefficient of ^{15 × 10 -6 / K~25 × 10} -6 / K α (20 ℃ ~300 ℃). A further advantage of the glass compositions shown above is that the glass can be melted in a gas atmosphere that is not a protective gas atmosphere, along with the light metal or metal of the conductor surrounding, especially in the form of metal pins. .. Unlike conventional methods, no vacuum is required for Al melting. Rather, such melting can also be done in air. _{N 2} or Ar can be utilized as the protective gas for both types of melting. As a pretreatment for melting, metals, especially light metals, are cleaned and / or etched if predetermined oxidation or coating is required. During the process, temperatures between 300 ° C and 600 ° C are used with heating rates of 0.1 to 30 C / min and holding times of 1 to 60 minutes.

Further, as illustrated in FIGS. 1a and 1b, the housing, battery or battery cell housing portion 5 is, in this case, a battery cover having an opening for penetrating the electrodes. The battery cover or housing portion is also preferably manufactured from aluminum. However, as materials for battery covers or housing parts, aluminum alloys, magnesium and magnesium alloys, AlSiC, titanium, titanium alloys, but also steel, stainless steel or specialty steels are also applicable. The housing portion has an outer 20.1 and an inner 20.2. The outside is characterized by extending outward from the battery cell, and the inside is characterized by extending to the electrolyte of the battery cell, for example, in the case of a lithium ion storage battery. The entire housing with battery cells and penetrations is shown in FIGS. 10a-12c.

In the case of lithium ion batteries, the electrolyte is typically a non-aqueous electrolyte, typically from a carbonate ester, especially a carbonate ester mixture, such as a non-aqueous electrolyte consisting of a mixture of ethylene carbonate and dimethyl carbonate. In that case, the corrosive, non-aqueous battery electrolyte has a conductive salt, such as the conductive salt LiPF ₆ , in the form of, for example, a 1 mol solution.

In the first embodiment, the support 3 has a protrusion 30. That is, in the example according to FIG. 1a, the wall thickness W1 of the ring-shaped body above the outside of the housing portion is thicker than the thickness W1 of the ring-shaped support 9 in the range inside the housing portion, thereby. An arrangement 32 of the support is formed on the outside of the ring-shaped body. The ring-shaped body 9 can be joined to the housing portion 5 by laser beam welding, electron beam welding, soldering, shrinking to the opening 7 and pushing into the opening 7 and flanged within the range of the arrangement portion 32. can.

FIG. 1b shows an example of a penetration portion similar to that of FIG. 1a, in which the same reference number is used for the same part.

However, in this case, the width W1 in the inner 20.2 range is larger than the width W2 in the outer 20.1 range.

In other respects, the morphology according to FIG. 1b is identical to that of FIG. 1a. As in the case of FIG. 1a, the joining is performed between the housing portion 5 which is the battery cover and the support 30 in this case, for example, to laser beam welding, electron beam welding, soldering, and opening 7 as described above. It can be done by shrinking or pushing in.

The support according to FIGS. 1a and 1b is essentially a flange ring, but in the form according to FIGS. 2a-2b, the ring-shaped support 109 is a ring-shaped support having a weld ring 170. The same parts as those in FIGS. 1a and 1b are indicated by reference numbers plus 100. In essence, the morphology according to FIGS. 2a-2b is identical to the morphology according to FIGS. 1a-1b. A ring-shaped support 109 having a welding ring 170 allows the support 109 to be joined to the housing portion by another joining method. The connection between the ring-shaped support and the housing portion within the range of the welding ring 170 can be performed by resistance welding or resistance soldering.

FIG. 3 shows a further embodiment of the present invention. The same parts as those in FIGS. 1a-1b and 2a-2b are indicated by reference numbers plus 200 for FIGS. 1a and 1b or 100 for FIGS. 2a-2b, respectively.

Unlike the form according to FIGS. 1a to 1b and 2a to 2b, the support does not have different widths W1 and W2 such that the stopper portion (Anschlag) 32 is formed, and the width W of the ring-shaped support is It is the same throughout the height. A ring-shaped support 209 having the same width over the entire height is introduced into the opening 207. The joint between the housing portion 205 and the penetration portion 203 including the ring-shaped support 209 and the glass material 213 and the essentially pin-shaped conductor 211 attaches to the opening 207, followed by the side wall 219 of the opening 207. Achieved by joining in the range, not by joining. The present invention can be manufactured by laser welding, soldering, shrinkage, indentation or electron welding.

4a-4c show another form of the penetration introduced into the opening 307 in the housing portion 305. In essence, this corresponds to the configuration according to FIG. 3, where a reference number plus 100 is used for the same part. However, unlike FIG. 3, the support 309 is formed as a conical ring that is inserted into the conical opening 307 within the housing portion. The joint between the penetrations is again performed between the side wall of the conical opening 307 and the conical support 309, for example by welding, soldering, flanging, shrinking. However, it is also possible to push the ring-shaped support 309, which extends essentially in a conical shape, into the conical opening 307 in the housing portion 305. The conical support can have the three forms shown in FIGS. 4a-4c. In FIG. 4a, the support is conical at the outer 395 with respect to the housing portion 305; in FIG. 4b, both the outer 395 and the inner 397 facing the pin-shaped conductor 311 are conical, and in FIG. 4c, the inner 397. Only conical. The conical shape of the support as well as the opening avoids the relative movement of the penetrating portion in the outer 320.1 direction of the housing portion 305. This is because the conical perforation and the conical support act as a so-called spear, and the relative movement in the outer 320.1 direction is the support 309 and opening 307 of the penetration 303. This is to provide a foam closure between the side wall and the wall.

The advantage of the form according to FIG. 4 is that even under a high load, for example, penetration of a pressure load, that is, penetration 303 having a metal pin 311 is reliably avoided from being pushed out of the penetration opening 307. It is particularly preferred to introduce the opening 307 into the housing portion 305 by a simple manufacturing method, for example by punching.

FIGS. 5 to 7 show the embodiment of the present invention in which the ring-shaped support 509 is also prepared in this case. However, in this case, the head portion 580 is provided on the pin-shaped conductor. The glass attachment in the form according to FIGS. 5a-5c and 6a-6b and 7 is a pin-shaped penetrating a ring-shaped support 509 that can be reattached to the housing portion, for example, as illustrated in FIG. Not only is it done between the conductors 511, but in this case the glass material or glass ceramic material 513 is also introduced between the support 509 and the head portion 580.

The dimension A1 of the head portion 580 is then essentially larger than the dimension A1 of the pin-shaped conductor 511. For conductors with an essentially circular cross section, the dimensions of the head portion are larger than the diameter of the pin-shaped conductor. This means that the head area of the head portion is larger than the head area of the pin-shaped conductor 511 to which the head portion 580 is joined. Further, the head portion 580 may be formed so that it can be joined to the electrode joining component. The electrode-joined parts are, in particular, copper parts at the cathode or aluminum parts at the anode. The head portion and the electrode joining component (not shown) are joined by mechanically stable, particularly inseparable electrical joining. Such mechanically stable and inseparable electrical joints weld head parts and electrode joint parts, especially resistance welding, electron beam welding, friction welding, ultrasonic welding, bonding, bonding, soldering, coking, It is provided by shrinking, grouting, clamping and pinching, preferably by tightly joining. After attaching the head portion 580 and the pin-shaped conductor 511 to the housing of the battery or the battery cell or attaching the glass, the head portion and the electrode joining component are joined. Of course, it would be possible to join the penetrating part to the electrode joint part before attaching it to the housing opening or glassing it, but the possibilities mentioned at the beginning are preferred.

The configuration with the head portion 580 provides a penetration that requires only a small amount of internal space when used within a housing for a battery cell. The head portion of the penetrating component according to the present invention has a very large integrated area for connecting the electrode joint components. This achieves high stability in the connection range. In particular, much higher flexural rigidity is achieved than connecting the electrode-joined parts directly to a pin-shaped conductor. A further advantage of connecting the electrode joints over the head portion is that narrowing or significant changes in cross-sectional area in the conductor path from the battery cell penetrating the battery cell housing are avoided over connecting directly to the pins. There is. Cross-sectional narrowing results in high heat loss, which can be problematic in battery cells, especially at high currents of 20A to 500A in lithium-ion batteries as energy carriers for automobiles. Such heat loss can be avoided by the head portion 580.

On the conductor, especially the pin-shaped conductor 511, a protrusion 582 protrudes into the battery cell, for example, on the inner side 520.2, and the protrusion 582 of the conductor makes the above-mentioned electrode joining component. Can help to center. The protrusions 582 of the pin-shaped conductor are preferably always formed in a circular shape, regardless of the shape of the conductor, which may be, for example, elliptical or circular. The protrusions and essentially pin-shaped conductors may also vary in size.

Alternatively, the ring-shaped support 509 can take an elliptical outer shape 590, as shown in different forms, eg, FIGS. 5a-5c, in which case the conductors preferably also have an elliptical support. In the penetrating range, i.e. in range 511, it may be similarly formed in an elliptical shape, but as shown in FIG. 5b, the head portion is circular in the perspective view to connect the electrode junction parts. ..

Instead of the elliptical embodiment of ring-shaped supports, pin-shaped conductors and protrusions, which is particularly advantageous for narrow battery covers, not only pin-shaped conductors but also centered protrusions and supports It can be formed in a ring shape. Of course, the morphology can be mixed, i.e. the elliptical support can be combined with the ring-shaped pin conductor, but it is not described in detail.

A ring-shaped support is shown in FIGS. 6a-6b along with a ring-shaped pin-shaped conductor. The same parts as those in FIGS. 5a-5c are indicated by reference numbers plus 100. That is, in FIGS. 6a to 6b, for example, reference number 611 indicates a pin-shaped conductor, 680 indicates a head portion, and 609 indicates a ring-shaped support.

In the embodiment according to FIG. 7, the head area 780 of the head portion 2 is auskragen, i.e. defined outside the diameter of the opening, in order to attach additional joints or joint parts to the electrodes. Is intended. The same parts as those in FIGS. 5a-5c are indicated by reference numbers plus 200. That is, the pin-shaped conductor has reference number 711, and the ring-shaped support has reference number 709. By extending the head portion 780 to the outside, it becomes possible to join by welding, resistance welding or riveting based on the fact that two surfaces can be utilized in addition to the above-mentioned joining method.

In particular, in the embodiment according to FIG. 7, the characteristic of the penetrating component according to the present invention that _{the area of the head portion 780 (F head portion} ) is larger than the area of the pin-shaped conductor 711 (F _{conductor) will be well understood.} In the embodiment according to FIG. 7, since the dimensions and the morphology of the protrusions of the pin-shaped conductor 711 are the same, the cross-sectional area of the protrusions shown in the perspective view is the same as the area of the pin-shaped conductors.

8a-9b show an embodiment of a penetration of a pin-shaped conductor passing through a support, wherein the housing portion, especially the penetration in the battery cover, is a thermal barrier and a mechanical unloading portion. Shown with.

8a and 8b show a first embodiment of a penetration portion according to the invention that has a unloading device for mechanical unloading and as a thermal barrier.

Unlike the embodiments according to FIGS. 1a-4, in the embodiments according to FIGS. 8a and 8b, the support 809 includes a ring-shaped notch 850 as a unloading device. Again, within the support 809 with the ring-shaped notch 850, the essentially pin-shaped conductor 811 is united with the glass or glass ceramic material 813.

Although not shown and not explicitly stated, in another embodiment, a pin-shaped conductor that also has a head portion may be formed, which does not require one of ordinary skill in the art.

Further, in FIG. 8a, it can be seen that the housing portion 805 is essentially a cover for the battery cell. Penetrations made of supports 809, essentially glazed with pin-shaped conductors, are joined to the housing portion 805 in a ring, eg, by laser welding, in a range of 870. The ring-shaped notch 850, on the one hand, is a thermal barrier and, on the other hand, provides the required elasticity to protect or unload the penetration, especially within the glassed 813 range. In particular, by introducing a ring-shaped notch 850, it is achieved to reduce the mechanical and thermal loads that occur in the glass or glass ceramic material. This can significantly reduce the formation of cracks in the glass material or glass ceramic material of the penetrations that can lead to leaks.

The form according to FIG. 8b also shows a penetrating portion having a ring-shaped notch 850 as a unloading device in the support. Unlike the form according to FIG. 8a, in this case, the housing portion 805 has 880 in the joining range between the penetration portion and the housing portion 805. This results in even better mechanical unloading than in the embodiment according to FIG. 8a. In addition, the support may be joined to the housing portion 805 over its full thickness D, which allows for an accurate welding process.

9a and 9b show a different embodiment than FIGS. 8a and 8b, in which the unloading and thermal barriers are also obtained in the case of FIGS. 9a and 9b. Unlike the embodiment according to FIG. 8a, the support in this case does not have a ring-shaped notch as a unloading device, but instead has a Ueverstand 990. The same parts as those in FIGS. 8a-8b are shown by reference numbers in FIGS. 8a and 8b plus 100. Therefore, pin-shaped conductors are shown at 911, and glass and glass ceramic materials are shown at 913. The joining range between the penetration and the housing portion is indicated by 970. The advantages of FIG. 8a as described above also apply to FIG. 9a, which are included together in this case.

FIG. 9b shows an embodiment different from that of FIG. 9a. In addition to the essentially ring-shaped support 909, in this case the cover portion 905 also has an overhang 980. The advantages of FIG. 8b as described above also apply to FIG. 9b, which are included together in this case.

All embodiments of FIGS. 8a-9b that provide mechanical and thermal unloading have head portions as detailed in FIGS. 5-7, instead of the illustrated embodiments having pin-shaped conductors 811. It is also possible to have a pin-shaped conductor. The disclosures of FIGS. 5-7 are broadly included together in this case without the need for special reference or illustration.

Figures 10a-11b show a complete battery cell for a lithium-ion battery fitted with a penetration according to the invention.

In this case, FIGS. 10a-10b show the embodiment of the present invention provided with a pin-shaped conductor having no head portion, that is, a through portion according to FIGS. 1a-4 or 9a-10b. In contrast, FIGS. 11a-11b show a battery cell with a housing and penetrations incorporated therein, wherein the pin-shaped conductor has a head portion according to the present invention.

FIG. 10a shows the basic structure of the battery cell 1000.

The battery cell 1000 has a housing 1100 with side walls 1110 and a cover portion 1120. The openings 1130.1 and 1130.2 are fitted into the cover portion 1120 of the housing 1100, for example, by punching. Penetrations 1140 and 1140.2 are reattached to both openings 1130.1 and 1130.2.

FIG. 10b shows in detail a portion of the battery cover 1120 with an opening 1130.1 and a penetration portion 1140.1 mounted therein.

Penetration 1140.1 includes a pin-shaped conductor 2003 and a support 2200. A pin-shaped conductor 2003 without a head portion is glassed in a support 2200 with a glass material or a glass ceramic material 2280. The pin-shaped conductor 2003 is attached to the support 2200 with glass or glass-ceramic material 2280 and then attached to the opening 1130.1 as a whole, for example, a through-through support preferably made of aluminum. The 2200 is joined to the cold-fixed cover portion 1120 made of aluminum, for example by welding. Based on the glazing, preferably only the support 2200 is softened.

The pin-shaped conductor is provided with a sampling portion (Ausnehmung) 2002, to which an electrode joining portion 2020 is attached. The electrode junction serves again as the cathode or anode of the electrochemical cell 2004 of the battery 1000. The housing 1100 surrounding the battery cell 1000 is referred to as a battery cell housing.

As can be seen from FIG. 10a, based on the design of the penetrations 1140.1, 1140.2, the pin-shaped conductor is attached to the pin-shaped conductor extraction part (Ausnehmung) 2002 and joined to the electrochemical cell 2004. The electrode-joined component is associated with a relatively large structural space 2006 formed between the electrochemical cell 2004 and the cover 1120.

The design of the penetration 3200 with pin-shaped conductors and head portions as shown in FIGS. 11a and 1b can minimize unused structural space in the battery cell housing. This can be clearly inferred in FIGS. 11a-11b.

The same parts in FIGS. 10a and 10b are indicated by reference numbers plus 2000.

Also in this case, the penetrations 3140.1 and 3140.2 are attached to the openings 3130.1 and 3130.2 of the cover 3120 of the battery cell housing 3100. Unlike the penetrating part of the penetrating portion shown in FIGS. 10a and 10b, the penetrating part is provided with a pin-shaped conductor 3003 and a head portion 3005. The head portion has a protrusion 3030 and an electrode joining component 3010 that is firmly mounted onto the head portion 3005 by welding, soldering or other methods described above. The electrode junction comprises a fragment 3140, wherein the fragment 3140 serves as a cathode or anode for the electrochemical cell 4004. As can be seen from FIGS. 11a-11b, the advantages of the penetrating parts according to the present invention should be clearly apparent. Due to the penetration structure types shown in FIGS. 11a-11b, the structural space within the battery cell housing that remains unused is as small as possible.

In essence, the morphology of the penetrations in FIGS. 11a and 11b is consistent with the morphology of the penetrations in FIGS. 6a-6b. The description of FIGS. 6a-6 is completely transferred to the description of the battery cell of the present invention.

12a-12c show a further form of the battery housing according to the invention with a penetration. The same parts as in the preceding figure are indicated by a reference number plus 5000. In the embodiments shown in FIGS. 12a-12c, the conductors, essentially pin-shaped conductors 7003.1, 7003.2, 7003.3, do not have a circular shape at the end on the battery cell side, i.e., for example. It does not have the circular cross section as shown in FIGS. 10a-11b, but rather has an essentially rectangular cross section 7100. Further, the conductors 7003.1, 7003.2 and 7003.3 have two bends. In principle, conductors 7003.1, 7003.2, 7003.3 already have a fragment 8110 at its end on the battery cell side, which serves as a cathode or anode for an electrochemical cell (not shown). Unlike the embodiments according to FIGS. 11a and 11b, in which another electrode joining component (shown by 3110 in FIG. 11b) is attached to the conductor, particularly the essentially pin-shaped conductor, by welding, for example, FIGS. 12a- The electrode joint component and the essentially pin-shaped conductor in the example according to 12c are integrally formed. This is advantageous from the point of view of preparation because it is not necessary to join the two parts. Embodiments 7003.1, 7003.2, 7003.3 are essentially different in the cross section of the conductor in the range of penetrations 8140.1, 8140.2, 8140.3. In the form according to FIG. 12a, the cross section of the conductor is also essentially rectangular in the range of the glassed 7280.

In the form according to FIG. 12b, the cross section is circular in the range of the glass-attached 7280 instead of the rectangular cross section. This conductor is indicated by reference number 7003.2. In the embodiment according to FIG. 12b, unlike the embodiment according to FIG. 12a, the conductor also has a circular cross section outside the battery cell.

In the form according to FIG. 12c, the cross section is circular in the range of the glassed 7280 as in FIG. 12b, but the conductor 7003.3 is squeezed in the connection range outside the battery housing and thus the cross section is rectangular, preferably square. Is. In all of FIGS. 12a-12c, the battery housing cover is indicated by 8120 and the support with the conductors 7003.1, 7003.2, 7003.3 glassed is indicated by 8130.

For the first time, the invention provides a housing that is prefabricated and particularly suitable for use within the housing portion of a battery cell housing, in particular a battery cell housing, preferably a penetration for a lithium ion battery. The battery cell housing preferably comprises a light metal such as aluminum (Al), aluminum alloy, AlSiC, magnesium, magnesium alloy, titanium or titanium alloy. However, as a material for the battery cell housing, metals such as steel or specialty steels, especially stainless steel or tool steel, are also possible. In such cases, the material of the support and / or essentially pin-shaped conductor is adapted.

The solution according to the present invention further makes it possible to use cost-effective manufacturing methods and starting materials. In addition, the entire penetration can be formed as a fixing material, i.e., a prefabricated component that is attached to the housing portion after the metal pins have been combined into the support by, for example, a glass stopper. This ensures that there is no loss of cold fixation of the housing parts. In addition, material strength and material can be selected independently of housing parts and supports. A special form of using a unloading device allows the penetration to be unloaded both mechanically and thermally.

The following are the initial claims of the international application (PCT / EP2012 / 000698) of the parent application (Japanese Patent Application No. 2013-553839) of the parental application of this application (Japanese Patent Application No. 2017-157386).
[Claim 1]
In particular a penetration (3) through the housing portion (5) of the housing, the housing being particularly a battery housing, preferably a metal, particularly a light metal, preferably an aluminum, aluminum alloy, AlSiC, magnesium, magnesium alloy, titanium. , Titanium alloy, steel, stainless steel or special steel, the housing portion (5) has at least one opening (7), and the opening (7) is in a glass material or a glass ceramic material. At least one of the conductors, especially the essentially pin-shaped conductor (11), penetrates.
The penetration (3) includes at least one conductor, particularly an essentially pin-shaped conductor (11) and a support (9), particularly an essentially ring-shaped support (9). Characteristic,
Penetration part (3).
[Claim 2]
The essentially pin-shaped conductor (11) is a material such as a metal, preferably copper, CuSiC, copper alloy, aluminum, AlSiC or aluminum alloy, magnesium or magnesium alloy, NiFe, NiFe-jacket having a copper interior. The support (9) includes silver, silver alloys, gold, gold alloys and cobalt-iron alloys, and the support (9) is a material particularly metal, preferably aluminum, AlSiC, aluminum alloy, steel, stainless steel, special steel, tool steel. , Magnesium or magnesium alloy, titanium or titanium alloy.
The penetration portion according to claim 1.
[Claim 3]
The support (109) is characterized by having a unloading device, particularly a notch (850) and / or an overhang (990).
The penetration portion according to any one of claims 1 and 2.
[Claim 4]
A glass material or a glass ceramic material is introduced between the support (9) and the conductor, particularly the pin-shaped conductor (11), in which the glass material or the glass ceramic material is preferably supported. It is characterized by having a melting temperature lower than the melting temperature of the body (9) and / or the conductor, particularly the pin (11).
The penetration portion according to any one of claims 1 to 3.
[Claim 5]
The glass material or the glass ceramic material is characterized by containing the following components in the following mol%.
The penetration portion according to any one of claims 1 to 4.
P ₂ O ₅ 35-50 mol%, especially 39-48 mol%,
Al ₂ O ₃ 0~14mol%, particularly 2~12mol%,
B ₂ O ₃ 2-10 mol%, especially 4-8 mol%,
Na ₂ O 0 to 30 mol%, especially 0 to 20 mol%,
M ₂ O 0 to 20 mol%, especially 12 to 20 mol% (where M = K, Cs, Rb may be),
PbO 0-10 mol%, especially 0-9 mol%,
Li ₂ O 0 to 45 mol%, particularly 0 to 20 mol%, particularly preferably 17 to 40 mol%,
BaO 0 to 20 mol%, especially 0 to 20 mol%, particularly preferably 5 to 20 mol%,
Bi ₂ O ₃ 0~10mol%, in particular 1 to 5 mol%, preferably 2~5mol%.
[Claim 6]
The composition comprises the following components in the following mol%:
The penetration portion according to any one of claims 1 to 5.
P ₂ O ₅ 38-50 mol%, especially 39-48 mol%,
Al ₂ O ₃ 3-14 mol%, especially 4-12 mol%,
B ₂ O ₃ 4-10 mol%, especially 4-8 mol%,
Na ₂ O 10-30 mol%, especially 14-20 mol%,
K ₂ O 10-20 mol%, especially 12-19 mol%,
PbO 0-10 mol%, especially 0-9 mol%.
[Claim 7]
The housing portion (5) has an outer side (20.1) and an inner side (20.2), and the support (5) is particularly welded or joined with the inner side and / or the outer side of the housing part. It is characterized in that it is joined in the form of a solder joint or by indentation.
The penetration portion according to any one of claims 1 to 6.
[Claim 8]
The pin-shaped conductor (511) includes a head portion (580), wherein the head portion has a head area (F _{head portion} ) _{larger than the area of the pin-shaped conductor (F conductor).} To
The penetration portion according to any one of claims 1 to 7.
[Claim 9]
The head portion (580) and / or the pin-shaped conductor has a circular or elliptical shape, and / or the glass or glass ceramic material (1013) is between the pin-shaped conductor and the support. However, on the other hand, it is also characterized by being introduced between the head portion and the support.
The penetration portion according to claim 8.
[Claim 10]
A housing comprising at least one penetration according to any one of claims 1-9, particularly for a battery cell (1000).
[Claim 11]
A battery housing, particularly a storage battery device having the housing according to claim 10, particularly a battery, preferably a Li-ion battery, particularly a Li-ion storage battery.
The storage battery device includes the penetrating portion according to any one of claims 1 to 9.
Storage battery device.
[Claim 12]
A method of manufacturing a penetration portion according to any one of claims 1 to 9, further comprising at least one conductor, particularly a pin-shaped conductor.
With the steps of preparing conductors, especially pin-shaped conductors and supports,
With the step of glassing a conductor, especially a pin-shaped conductor, into a support in glass or glass ceramic material to create a penetration for the housing portion of the housing, especially the battery cell housing.
How to include.
[Claim 13]
The glass material or the glass ceramic material is characterized by containing the following components in the following mol%.
12. The method of claim 12.
P ₂ O ₅ 35-50 mol%, especially 39-48 mol%,
Al ₂ O ₃ 0~14mol%, particularly 2~12mol%,
B ₂ O ₃ 2-10 mol%, especially 4-8 mol%,
Na ₂ O 0 to 30 mol%, especially 0 to 20 mol%,
M ₂ O 0 to 20 mol%, especially 12 to 20 mol% (where M = K, Cs, Rb may be),
PbO 0-10 mol%, especially 0-9 mol%,
Li ₂ O 0 to 45 mol%, especially 0 to 40 mol%, preferably 17 to 40 mol%,
BaO 0 to 20 mol%, especially 0 to 20 mol%, preferably 5 to 20 mol%,
Bi ₂ O ₃ 0~10mol%, in particular 1 to 5 mol%, preferably 2~5mol%.
[Claim 14]
The glass material or the glass ceramic material is characterized by containing the following components in the following mol%.
13. The method of claim 13.
P ₂ O ₅ 38-50 mol%, especially 39-48 mol%,
Al ₂ O ₃ 3-14 mol%, especially 4-12 mol%,
B ₂ O ₃ 4-10 mol%, especially 4-8 mol%,
Na ₂ O 10-30 mol%, especially 14-20 mol%,
K ₂ O 10-20 mol%, especially 12-19 mol%,
PbO 0-10 mol%, especially 0-9 mol%.
[Claim 15]
In particular, a method for providing a battery cell (1000) having the penetration portion according to any one of claims 1 to 9.
Steps to prepare a penetration with a support,
With the step of glassing a conductor, especially a pin-shaped conductor, into a support in a glass or glass ceramic material to create the penetration.
Steps to join the penetration to the housing, especially by welding, preferably laser beam welding, electron beam welding, ultrasonic welding, resistance welding, and otherwise by soldering, shrinking, pushing, and flanged.
How to include.

Claims (25)

A housing portion (5) of a power storage device having a side wall and a cover portion made of metal.
The cover portion has at least one opening (7).
The housing portion (5) comprises a penetration portion (3) disposed within the at least one opening (7).
The penetrating portion (3) is
One of the glass materials and glass ceramic materials,
The glass material and at least one pin-shaped conductor (11) embedded in the one of the glass ceramic materials.
Ring-shaped support (9) and
Including
The glass material and the at least one pin-shaped conductor (11) embedded in the one of the glass ceramic materials are guided through the support (9).
The ring-shaped support (9) within the region of the opening (7) is hermetically sealed to the housing portion (5) by one of welding, soldering, pushing, flanging and shrinking, and helium. leak rate state, and are less than 1 × ¹⁰ 8 mbarl / sec,
The ring-shaped support (9) includes a unloading device.
Housing part (5). The pin-shaped conductor (11) is a light metal.
The housing portion (5) according to claim 1. The metal of the pin-shaped conductor (11) is copper, CuSiC, copper alloy, aluminum, AlSiC, aluminum alloy, magnesium, magnesium alloy, NiFe, NiFe jacket having a copper interior, silver, silver alloy, gold, gold alloy or With cobalt-iron alloy,
The housing portion (5) according to claim 1 or 2. The housing portion (5) includes a light metal.
The housing portion (5) according to any one of claims 1 to 3. The light metal of the housing portion (5) comprises aluminum, AlSiC, an aluminum alloy, magnesium, a magnesium alloy, titanium or a titanium alloy.
The housing portion (5) according to claim 4. The ring-shaped support (9) is made of aluminum, aluminum alloy, AlSiC, steel, stainless steel, special steel, magnesium, magnesium alloy, titanium, titanium alloy.
The housing portion (5) according to any one of claims 1 to 5. The ring-shaped support (9) comprises grooves and / or protrusions.
The housing portion (5) according to any one of claims 1 to 6. The glass material or the glass ceramic material is introduced between the ring-shaped support (9) and the pin-shaped conductor (11), whereby the glass material or the glass ceramic material is the ring. It has a sealing temperature lower than the melting temperature of the shaped support (9) and / or the pin-shaped conductor (11).
The housing portion (5) according to any one of claims 1 to 7. The glass material or the glass ceramic material contains the following components in the following molar%:
P ₂ O ₅ 35-50 mol%,
Al ₂ O ₃ 0~14mol%,
B ₂ O ₃ 2-10 mol%,
Na ₂ O 0 to 30 mol%,
M ₂ O 0 to 20 mol%, where M = K, Cs, Rb.
PbO 0-10 mol%,
Li ₂ O 0-45 mol%,
BaO 0-20 mol%,
Bi ₂ O ₃ 0~10mol%,
The housing portion (5) according to any one of claims 1 to 8. The glass material or the glass ceramic material contains the following components in the following molar%:
P ₂ O ₅ 39-48 mol%,
Al ₂ O ₃ 2-12 mol%,
B ₂ O ₃ 4-8 mol%,
Na ₂ O 0 to 20 mol%,
M ₂ O 12-20 mol%, where M = K, Cs, Rb.
PbO 0-9 mol%,
Li ₂ O 0-40 mol%,
BaO 0-20 mol%,
Bi ₂ O ₃ 1-5 mol%,
The housing portion (5) according to claim 9. The glass material or the glass ceramic material contains the following components in the following molar%:
Li ₂ O 17-40 mol%,
BaO 5-20 mol%,
Bi ₂ O ₃ 2-5 mol%,
The housing portion (5) according to claim 9 or 10. The glass material or the glass ceramic material contains the following components in the following molar%:
P ₂ O ₅ 38-50 mol%,
Al ₂ O ₃ 3-14 mol%,
B ₂ O ₃ 4-10 mol%,
Na ₂ O 10-30 mol%,
K ₂ O 10 to 20 mol%,
PbO 0-10 mol%,
The housing portion (5) according to claim 9. The glass material or the glass ceramic material contains the following components in the following molar%:
P ₂ O ₅ 39-48 mol%,
Al ₂ O ₃ 4-12 mol%,
B ₂ O ₃ 4-8 mol%,
Na ₂ O 14 to 20 mol%,
K ₂ O 12-19 mol%,
PbO 0-9 mol%,
12. The housing portion (5) according to claim 12. The housing portion (5) has an outer side and an inner side, and the ring-shaped support (9) is in the form of a welded joint or a soldered joint, or by pushing, the inner side or the inner side of the housing part (5). Joined to the outside,
The housing portion (5) according to any one of claims 1 to 13. The pin-shaped conductor (11) comprises a head portion, whereby the head portion has a head area (F _{head portion} ) that is _{larger than the area (F conductor) of the pin-shaped conductor (11).}
The housing portion (5) according to any one of claims 1 to 14. The head portion and / or the pin-shaped conductor (11) has a circular or elliptical outer shape, and / or the glass material or the glass ceramic material is, on the one hand, the pin-shaped conductor (11). ) And the ring-shaped support (9), and on the other hand, it is placed between the head portion and the ring-shaped support (9).
The housing portion (5) according to claim 15. A power storage device including the housing portion (5) according to any one of claims 1 to 16. The power storage device is a battery or a lithium ion storage battery.
The power storage device according to claim 17. The method for manufacturing a housing portion (5) according to any one of claims 1 to 9 and 14 to 16, which has at least one pin-shaped conductor (11).
-With the steps of providing the pin-shaped conductor (11) and the ring-shaped support (9).
-The pin-shaped conductor (11) is sealed and embedded in the glass material or glass ceramic material in the ring-shaped support (9), and the housing portion (5) of the housing of the power storage device is formed. The step resulting in the penetration (3) for
- welding, laser welding, electron beam welding, ultrasonic welding, resistance welding, and, in the alternative, soldering, shrinking, by pushing or flanging, gas helium leak rate of less than 1 × 10 ⁸ mbarl / sec A step of joining the penetrating portion (3) to the housing by a tight sealing method, and
How to include. The housing of the power storage device is a battery cell housing or a Li-ion storage battery housing.
19. The method of claim 19. The glass material or the glass ceramic material contains the following components in the following molar%:
P ₂ O ₅ 35-50 mol%,
Al ₂ O ₃ 0~14mol%,
B ₂ O ₃ 2-10 mol%,
Na ₂ O 0 to 30 mol%,
M ₂ O 0 to 20 mol%, where M = K, Cs, Rb.
PbO 0-10 mol%,
Li ₂ O 0-45 mol%,
BaO 0-20 mol%,
Bi ₂ O ₃ 0~10mol%,
The method of claim 19 or 20. The glass material or the glass ceramic material contains the following components in the following molar%:
P ₂ O ₅ 39-48 mol%,
Al ₂ O ₃ 2-12 mol%,
B ₂ O ₃ 4-8 mol%,
Na ₂ O 0 to 20 mol%,
M ₂ O 12-20 mol%, where M = K, Cs, Rb.
PbO 0-9 mol%,
Li ₂ O 0-40 mol%,
BaO 0-20 mol%,
Bi ₂ O ₃ 1-5 mol%,
21. The method of claim 21. The glass material or the glass ceramic material contains the following components in the following molar%:
Li ₂ O 17-40 mol%,
BaO 5-20 mol%,
Bi ₂ O ₃ 2-5 mol%,
The method of claim 21 or 22. The glass material or the glass ceramic material contains the following components in the following molar%:
P ₂ O ₅ 38-50 mol%,
Al ₂ O ₃ 3-14 mol%,
B ₂ O ₃ 4-10 mol%,
Na ₂ O 10-30 mol%,
K ₂ O 10 to 20 mol%,
PbO 0-10 mol%,
21. The method of claim 21. The glass material or the glass ceramic material contains the following components in the following molar%:
P ₂ O ₅ 39-48 mol%,
Al ₂ O ₃ 4-12 mol%,
B ₂ O ₃ 4-8 mol%,
Na ₂ O 14 to 20 mol%,
K ₂ O 12-19 mol%,
PbO 0-9 mol%,
24. The method of claim 24.

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